CN1557978A - Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method - Google Patents
Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method Download PDFInfo
- Publication number
- CN1557978A CN1557978A CNA2004100217255A CN200410021725A CN1557978A CN 1557978 A CN1557978 A CN 1557978A CN A2004100217255 A CNA2004100217255 A CN A2004100217255A CN 200410021725 A CN200410021725 A CN 200410021725A CN 1557978 A CN1557978 A CN 1557978A
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- vanadium
- sodium
- amount
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000011733 molybdenum Substances 0.000 title claims abstract description 97
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 97
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000011734 sodium Substances 0.000 claims abstract description 40
- 238000001556 precipitation Methods 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 29
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000005303 weighing Methods 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 38
- 238000001914 filtration Methods 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims description 19
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 19
- 239000000292 calcium oxide Substances 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 17
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 17
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910004647 CaMoO4 Inorganic materials 0.000 claims description 7
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 2
- 159000000007 calcium salts Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010446 mirabilite Substances 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 238000003801 milling Methods 0.000 abstract 1
- 239000005078 molybdenum compound Substances 0.000 abstract 1
- 150000002752 molybdenum compounds Chemical class 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 15
- 239000002893 slag Substances 0.000 description 9
- 239000011575 calcium Substances 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 229910001948 sodium oxide Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910019501 NaVO3 Inorganic materials 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- DIMMBYOINZRKMD-UHFFFAOYSA-N vanadium(5+) Chemical compound [V+5] DIMMBYOINZRKMD-UHFFFAOYSA-N 0.000 description 4
- 229910001182 Mo alloy Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000756 V alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Catalysts (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a production process for extracting vanadium and molybdenum from a waste aluminum-based molybdenum catalyst by a wet method, which is sequentially carried out according to the steps of raw material ball milling, material mixing weighing, sodium roasting, water milling hot dipping, dephosphorization purification, vanadium precipitation and molybdenum precipitation and extraction: the method comprises the steps of carrying out sodium roasting reaction on a waste aluminum-based molybdenum catalyst containing vanadium and molybdenum elements, matched with mirabilite, soda ash and industrial salt, preparing a mixed solution containing vanadium and molybdenum compounds by a water mill hot leaching mode, carrying out dephosphorization purification treatment, and respectively carrying out precipitation separation by using ammonium salt and calcium salt to extract vanadium and molybdenum. The invention realizes the purpose of simultaneously extracting precious vanadium and molybdenum products on the basis of utilizing the existing wet vanadium extraction process and production equipment, and has extremely high economic value. The invention has novel conception, simple and convenient process and very obvious economic benefit and social environmental protection effect.
Description
The technical field is as follows:
the invention relates to the technical field of metallurgy, in particular to a production technology for extracting metal by wet separation, and specifically relates to a production technology for extracting vanadium and molybdenum from a waste aluminum-based molybdenum catalyst by a wet method.
Background art:
vanadium and molybdenum are known to be very important alloying elements. The vanadium and molybdenum alloy material has very good mechanical properties, so that the vanadium and molybdenum alloy material has very wide application in numerous technical fields of mechanical manufacturing, casting processing, aerospace, instruments and meters, military industry, other high-tech and the like, and the vanadium and molybdenum alloy material plays an extremely important role in national economic construction and national defense and military construction in China. However, in our country, the vanadium and molybdenum mineral resources are scarce objectively, and how to develop and utilize the precious vanadium and molybdenum resources scientifically, reasonably, economically and has very important economic strategic significance. At present, in the petrochemical industry, the crude oil is mostly desulfurized byadopting an aluminum-based molybdenum catalyst, and in the process of crude oil desulfurization, the aluminum-based molybdenum catalyst can adsorb a large amount of elements such as vanadium, sulfur, phosphorus and the like from the crude oil to generate low-valent vanadium (such as VS and V)2S3) Molybdenum sulfide (MoS)2) And phosphorus-containing compounds and other impurities, so that the aluminum-based molybdenum catalyst is poisoned and loses efficacy and becomes waste aluminum-based molybdenum catalyst to be discarded. At present, the quantity of the aluminum-based molybdenum catalyst discarded every year in the petroleum production industry of various countries in the world is very large, and the aluminum-based molybdenum catalyst is accumulated like a mountain in the long run, so that the aluminum-based molybdenum catalyst becomes waste residue pollution and seriously damages the surrounding ecological environment. According to the determination: the discarded waste aluminum-based molybdenum catalyst contains V2O5About 16 percent, about 4.5 percent of nickel, about 4.5 percent of molybdenum and about 0.01 percent of phosphorus, which is the valuable vanadium and molybdenum resource which is urgently needed to be developed and utilized by the metallurgical department. Chinese patent CN1321782A discloses an invention patent application (patent application No. 00112900.7) named as a wet-process vanadium extraction process from waste aluminum-based molybdenum catalyst, which adopts the traditional wet-process metallurgy technology, mixes the waste aluminum-based molybdenum catalyst with limestone and mirabilite, adds water and ball-mills to prepare mixed slurry, and then sends the mixed slurry into a rotary kiln for calcification roasting to generate calcium vanadate Ca (VO)3)2Calcium molybdate CaMoO4And calcium phosphate Ca3(PO4)2The mixture clinker is treated with sodium carbonate Na2CO3The solution is leached and carbonated, and the leaching solution of vanadium can be obtained by separation. Although the technology of the wet vanadium extraction process from the waste aluminum-based molybdenum catalyst can separate and extract vanadium element and can better solve the serious problem of waste residue pollution formed in the petroleum industry for years. However, when the leaching solution for preparing vanadium by separating in the leaching carbonation reaction is carried out by adopting the method, the calcium molybdate CaMoO is used as the precious molybdenum element with the content of about 4.5 percent4The sediment is fixed in the residue and is discharged along with the residue, which is a great waste of precious molybdenum resources.
The invention content is as follows:
the invention provides a production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by a wet method on the basis of the existing wet vanadium extraction process and equipment, which has the advantages of simple process, advanced technology and low production cost, can economically and reasonably separate and extract precious vanadium and molybdenum products from the waste aluminum-based molybdenum catalyst at the same time, and better solves the serious problem of waste residue pollution formed in the petroleum industry for a long time. Has obvious economic benefit and environmental protection effect, and is realized by the following technical scheme:
the method comprises the following steps in sequence:
(1) ball milling of raw materials: carrying out surface deoiling treatment on the waste aluminum-based molybdenum catalyst material, and then sending the material into a ball mill for ball milling to obtain powder, wherein the particle size of the waste aluminum-based molybdenum catalyst powder is controlled to be 40-120 meshes;
(2) weighing and mixing materials: the raw materials in the specified proportion (by weight):
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
sodium carbonate (Na)2CO3) 0.1-0.65 portion,
natrii sulfas (Na)2SO4) 0.1-0.65 portion,
0.1-0.65 portion of industrial salt (NaCl),
respectively weighing the materials, feeding the materials into a spiral mixer, and mixing to obtain mixed materials;
(3) sodium treatment roasting: the mixed material is sent into the rotary kiln by a disc feeder to carry out sodium roasting reaction, the roasting temperature is controlled between 950 and 1050 ℃, the roasting time is controlled between 2 and 3 hours,
the following oxidation-sodium roasting reactions are carried out in a rotary kiln:
low-valence vanadium (such as VS and V) contained in waste aluminum-based molybdenum catalyst2S3) Is first oxidized into high-valence vanadium (V)2O5)：
MoS contained in waste aluminium-based molybdenum catalyst2First oxidized to MoO3
V formed by oxidation2O5And MoO3Then carrying out the following sodium treatment reaction:
after the industrial salt is oxidized to generate sodium oxide, the sodium oxide is mixed with V2O5And MoO3Carrying out sodium treatment:
after the oxidation-sodium roasting reaction, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The mixed clinker of (4);
(4) grinding with water and hot dipping: the prepared mixed clinker is sent into a water ball mill, hot water is added for water ball milling hot leaching, and the NaVO containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The water adding amount of the mixed solution is controlled to be 3-4 times of the total weight of the solid matters of the mixed clinker, the hot dipping temperature is controlled to be 50-90 ℃, and the residual slag filtered by the horizontal belt type vacuum filter after being subjected to hot dipping by the water ball mill can be used as secondary slag to be returned to the weighing and mixing step for recycling, so that the extraction rate of vanadium and molybdenum can be effectively improved;
(5) dephosphorization and purification: the prepared sodium metavanadate NaVO3And sodium molybdate Na2MoO4The mixed solution is input into a dephosphorization sedimentation tank, and calcium chloride CaCl is added according to the volume-weight proportion of 1-5 kg/cubic meter of the mixed solution2Carrying out a phosphorus precipitation reaction:
concentrating, filtering and discarding to generate calcium phosphate Ca by a concentrator3(PO4)2After the slag is settled, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The concentrated mixed solution is input into a liquid storage tank for further clarification and purification;
(6) precipitating and extracting vanadium: inputting the clarified and purified concentrated mixed solution into a vanadium precipitation tank, and adding ammonium chloride NH under the stirring working condition4Cl is subjected to vanadium precipitation reaction, and ammonium chloride NH is controlled4The amount of Cl added is the amount of V contained (in terms of V) in the concentrated mixed solution2O5The amount of (b) is 2.0-3.0 times of that of basic weight),
filtering to obtain ammonium metavanadate NH4VO3Precipitating the product;
(7) precipitating and extracting molybdenum: filtering and separating ammonium metavanadate NH4VO3Inputting the mother liquor after precipitating the product into a molybdenum precipitation tank, and adding calcium salt (Ca) under stirring condition2+) Carrying out molybdenum precipitation reaction, such as: adding calcium oxide CaO under stirring condition to perform molybdenum precipitation reaction, controlling the addition amount of the calcium oxide CaO to be 0.7-1.2 times of the molybdenum content (calculated by the weight of Mo) in the mother liquor,
filtering to obtain calcium molybdate CaMoO4The product is precipitated.
The invention also has the following technical characteristics:
in the step of weighing and mixing materials, the raw materials can also be mixed according to the following proportion (by weight):
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
natrii sulfas (Na)2SO4) 0.8-0.9 portion,
weighing materials, feeding the weighed materials into a spiral mixer, and mixing the materials into a mixed material;
in the step of precipitating and extracting molybdenum, calcium chloride CaCl can also be added under the stirring condition2Carrying out the following molybdenum precipitation reaction, controlling calcium chloride CaCl2The adding amount of the molybdenum-containing agent is 1-1.5 times of the molybdenum-containing amount (calculated by the weight of Mo-containing agent) in the mother liquor,
filtering to obtain calcium molybdate CaMoO4The product is precipitated.
Description of the drawings:
the attached drawing is a production flow chart of the invention.
The specific implementation mode is as follows:
the first embodiment is as follows:
the method comprises the following steps in sequence:
(1) ball milling of raw materials: carrying out surface deoiling treatment on the waste aluminum-based molybdenum catalyst material, feeding the material into a ball mill, and ball-milling the material into powder, wherein the granularity of the waste aluminum-based molybdenum catalyst powder is controlled to be 80 meshes;
(2) weighing and mixing materials: the raw materials in the specified proportion (by weight):
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
sodium carbonate (Na)2CO3) 0.4 part by weight of a reaction kettle,
natrii sulfas (Na)2SO4) 0.4 part by weight of a reaction kettle,
0.4 part of industrial salt (NaCl),
respectively weighing the materials, feeding the materials into a spiral mixer, and mixing to obtain mixed materials;
(3) sodium treatment roasting: the mixed material is sent into a rotary kiln by a disc feeder to carry out sodium treatment roasting reaction, the roasting temperature is controlled to be 1000 ℃, the roasting time is controlled to be 2.5 hours,
the following oxidation-sodium roasting reactions are carried out in a rotary kiln:
low-valence vanadium (such as VS and V) contained in waste aluminum-based molybdenum catalyst2S3) Is first oxidized into high-valence vanadium (V)2O5)：
MoS contained in waste aluminium-based molybdenum catalyst2First oxidized to MoO3
V formed by oxidation2O5And MoO3Then carrying out the following sodium treatment reaction:
after the industrial salt is oxidized to generate sodium oxide, the sodium oxide is mixed with V2O5And MoO3Carrying out sodium treatment:
after the oxidation-sodium roasting reaction, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The mixed clinker of (4);
(4) grinding with water and hot dipping: the prepared mixed clinker is sent into a water ball mill, hot water is added for water ball milling hot leaching, and the NaVO containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The water adding amount of the mixed solution is controlled to be 3.5 times of the total weight of solid matters of the mixed clinker, the hot dipping temperature is controlled to be 70 ℃, the residual slag filtered by a horizontal belt type vacuum filter after being subjected to hot dipping by a water ball mill can be returned to a weighing and mixing step as secondary slag for recycling, and the extraction rate of vanadium and molybdenum can be effectively improved;
(5) dephosphorization and purification: the prepared sodium metavanadate NaVO3And sodium molybdate Na2MoO4The mixed solution is input into a dephosphorization sedimentation tank, and the mixed solution is mixed according to the proportion of 3 kg/cubic meterAdding calcium chloride CaCl according to volume-weight ratio2Carrying out a phosphorus precipitation reaction:
concentrating, filtering and discarding to generate calcium phosphate Ca by a concentrator3(PO4)2After the slag is settled, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The concentrated mixed solution is input into a liquid storage tank for further clarification and purification;
(6) precipitating and extracting vanadium: inputting the clarified and purified concentrated mixed solution into a vanadium precipitation tank, and adding ammonium chloride NH under the stirring working condition4Cl is subjected to vanadium precipitation reaction, and ammonium chloride NH is controlled4The amount of Cl added is the amount of V contained (in terms of V) in the concentrated mixed solution2O5In an amount of 2.5 times the reference weight),
filtering to obtain ammonium metavanadate NH4VO3Precipitating the product;
(7) precipitating and extracting molybdenum: filtering and separating ammonium metavanadate NH4VO3Inputting the mother liquor after the product precipitation into a molybdenum precipitation tank, adding calcium oxide CaO under the stirring condition to carry out molybdenum precipitation reaction, controlling the addition amount of the calcium oxide CaO to be 1.0 time of the molybdenum content (calculated by taking the amount of Mo as a reference weight) in the mother liquor,
filtering to obtain calcium molybdate CaMoO4The product is precipitated.
Example two:
the method comprises the following steps in sequence:
(1) ball milling of raw materials: carrying out surface deoiling treatment on the waste aluminum-based molybdenum catalyst material, feeding the material into a ball mill, and ball-milling the material into powder, wherein the granularity of the waste aluminum-based molybdenum catalyst powder is controlled to be 120 meshes;
(2) weighing and mixing materials: the raw materials in the specified proportion (by weight):
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
sodium carbonate (Na)2CO3) 0.65 part by weight of a reaction kettle,
natrii sulfas (Na)2SO4) 0.65 part by weight of a reaction kettle,
0.65 portion of industrial salt (NaCl),
respectively weighing the materials, feeding the materials into a spiral mixer, and mixing to obtain mixed materials;
(3) sodium treatment roasting: the mixed material is sent into a rotary kiln by a disc feeder to carry out sodium treatment roasting reaction, the roasting temperature is controlled to 1050 ℃, the roasting time is controlled to 3 hours,
the following oxidation-sodium roasting reactions are carried out in a rotary kiln:
low-valence vanadium (such as VS and V) contained in waste aluminum-based molybdenum catalyst2S3) Is first oxidized into high-valence vanadium (V)2O5)：
MoS contained in waste aluminium-based molybdenum catalyst2First oxidized to MoO3
V formed by oxidation2O5And MoO3Then carrying out the following sodium treatment reaction:
after the industrial salt is oxidized to generate sodium oxide, the sodium oxide is mixed with V2O5And MoO3Carrying out sodium treatment:
after the oxidation-sodium roasting reaction, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The mixed clinker of (4);
(4) grinding with water and hot dipping: the prepared mixed clinker is sent into a water ball mill, hot water is added for water ball milling hot leaching, and the NaVO containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The water adding amount of the mixed solution is controlled to be 4 times of the total weight of solid matters of the mixed clinker, the hot dipping temperature is controlled to be 90 ℃, and the residual slag filtered by a horizontal belt type vacuum filter after being subjected to water ball milling and hot dipping can be returned to a weighing and mixing step as secondary slag for recycling, so that the extraction rate of vanadium and molybdenum can be effectively improved;
(5) dephosphorization and purification: the prepared sodium metavanadate NaVO3And sodium molybdate Na2MoO4The mixed solution is input into adephosphorization sedimentation tank, and calcium chloride CaCl is added according to the volume weight proportion of 5 kg/cubic meter of the mixed solution2Carrying out a phosphorus precipitation reaction:
concentrating, filtering and discarding to generate calcium phosphate Ca by a concentrator3(PO4)2After the slag is settled, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The concentrated mixed solution is input into a liquid storage tank for further clarification and purification;
(6) precipitation extractionVanadium: inputting the clarified and purified concentrated mixed solution into a vanadium precipitation tank, and adding ammonium chloride NH under the stirring working condition4Cl is subjected to vanadium precipitation reaction, and ammonium chloride NH is controlled4The amount of Cl added is the amount of V contained (in terms of V) in the concentrated mixed solution2O5In an amount based on the weight) of 3.0 times,
filtering to obtain ammonium metavanadate NH4VO3Precipitating the product;
(7) precipitating and extracting molybdenum: filtering and separating ammonium metavanadate NH4VO3Inputting the mother liquor after the product precipitation into a molybdenum precipitation tank, adding calcium oxide CaO under the stirring condition to carry out molybdenum precipitation reaction, controlling the addition amount of the calcium oxide CaO to be 1.2 times of the molybdenum content (calculated by taking the amount of Mo as a reference weight) in the mother liquor,
filtering to obtain calcium molybdate CaMoO4The product is precipitated.
Example three:
the method comprises the following steps in sequence:
(1) ball milling of raw materials: carrying out surface deoiling treatment on the waste aluminum-based molybdenum catalyst material, feeding the material into a ball mill, and ball-milling the material into powder, wherein the granularity of the waste aluminum-based molybdenum catalyst powder is controlled to be 40 meshes;
(2) weighing and mixing materials: the raw materials in the specified proportion (by weight):
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
natrii sulfas (Na)2SO4) 0.85 part by weight of a reaction kettle,
respectively weighing the materials, feeding the materials into a spiral mixer, and mixing to obtain mixed materials;
(3) sodium treatment roasting: the mixed material is sent into a rotary kiln by a disc feeder to carry out sodium treatment roasting reaction, the roasting temperature is controlled to be 950 ℃, the roasting time is controlled to be 2 hours,
the following oxidation-sodium roasting reactions are carried out in a rotary kiln:
low-valence vanadium (such as VS and V) contained in waste aluminum-based molybdenum catalyst2S3) Is first oxidized into high-valence vanadium (V)2O5)：
MoS contained in waste aluminium-based molybdenum catalyst2First oxidized to MoO3
V formed by oxidation2O5And MoO3Then carrying out the following sodium treatment reaction:
after the oxidation-sodium roasting reaction, NaVO mainly containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The mixed clinker of (4);
(4) grinding with water and hot dipping: the prepared mixed clinker is sent into a water ball mill, hot water is added for water ball milling hot leaching, and the NaVO containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The water adding amount of the mixed solution is controlled to be 3 times of the total weight of solid matters of the mixed clinker, and the hot dipping temperature is controlled to be 50 ℃;
(5) dephosphorization and purification: the prepared sodium metavanadate NaVO3And sodium molybdate Na2MoO4The mixed solution is input into a dephosphorization sedimentation tank, and calcium chloride CaCl is added according to the volume weight proportion of 1 kg/cubic meter of the mixed solution2Carrying out a phosphorus precipitation reaction:
concentrating, filtering and discarding to generate phosphorus by a concentratorCalcium Ca3(PO4)2After settling, the main product is obtainedNaVO containing sodium metavanadate3And sodium molybdate Na2MoO4The concentrated mixed solution is input into a liquid storage tank for further clarification and purification;
(6) precipitating and extracting vanadium: inputting the clarified and purified concentrated mixed solution into a vanadium precipitation tank, and adding ammonium chloride NH under the stirring working condition4Cl is subjected to vanadium precipitation reaction, and ammonium chloride NH is controlled4The amount of Cl added is the amount of V contained (in terms of V) in the concentrated mixed solution2O5In an amount of 2.0 times the reference weight),
filtering to obtain ammonium metavanadate NH4VO3Precipitating the product;
(7) precipitating and extracting molybdenum: filtering and separating ammonium metavanadate NH4VO3Inputting mother liquor after product precipitation into a molybdenum precipitation tank, and adding calcium chloride CaCl under stirring condition2Performing molybdenum precipitation reaction to control calcium oxide CaCl2The adding amount is 1.2 times of the molybdenum content (calculated by the weight of Mo content as reference) in the mother liquor,
filtering to obtain calcium molybdate CaMoO4And precipitating the product, so as to realize the purpose of simultaneously separating and extracting vanadiumand molybdenum.
Claims (3)
1. A production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by a wet method sequentially comprises the following steps:
(1) ball milling of raw materials: carrying out surface deoiling treatment on the waste aluminum-based molybdenum catalyst material, and then sending the material into a ball mill for ball milling to obtain powder, wherein the particle size of the waste aluminum-based molybdenum catalyst powder is controlled to be 40-120 meshes;
(2) weighing and mixing materials: according to the specified raw material proportion (by weight), respectively weighing materials, feeding the materials into a spiral mixer, and mixing to prepare a mixed material;
the method is characterized in that:
in the step of weighing and mixing the materials, the specified raw material ratio (by weight) is as follows:
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
sodium carbonate (Na)2CO3) 0.1-0.65 portion,
natrii sulfas (Na)2SO4) 0.1-0.65 portion,
0.1-0.65 portion of industrial salt (NaCl),
(3) sodium treatment roasting: the mixed material is delivered into a rotary kiln for sodium roasting reaction, the roasting temperature is controlled to 950-1050 ℃, the roasting time is 2-3 hours, and the NaVO containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The mixed clinker of (4);
(4) grinding with water and hot dipping: the prepared mixed clinker is sent into a water ball mill, hot water is added for water ball milling hot leaching, and the NaVO containing sodium metavanadate is prepared3And sodium molybdate Na2MoO4The water adding amount of the mixed solution is controlled to be 3-4 times of the total weight of the solid matters of the mixed clinker, and the hot dipping temperature is controlled to be 50-90 ℃;
(5) dephosphorization and purification: inputting the prepared mixed solution into a dephosphorization sedimentation tank, and adding calcium chloride CaCl according to the volume-weight proportion of 1-5 kg/cubic meter of the mixed solution2Carrying out a phosphorus precipitation reaction, concentrating, filtering and deslagging by a concentrator to obtain NaVO mainly containing sodium metavanadate3And sodium molybdate Na2MoO4The concentrated mixed solution of (1);
(6) precipitating and extracting vanadium: inputting the concentrated mixed solution into a vanadium precipitation tank, and adding ammonium chloride NH under the stirring working condition4Cl is subjected to vanadium precipitation reaction, and ammonium chloride NH is controlled4The amount of Cl added is the amount of V contained (in terms of V) in the concentrated mixed solution2O5The amount of the ammonium metavanadate is 2.0-3.0 times of the reference weight), and the ammonium metavanadate NH is prepared after filtration4VO3Producing a product;
(7) precipitating and extracting molybdenum: filtering and separating ammonium metavanadate NH4VO3Inputting the mother liquor after precipitating the product into a molybdenum precipitation tank, adding calcium oxide CaO under the stirring condition to carry out molybdenum precipitation reaction, controlling the adding amount of the calcium oxide CaO to be 0.7-1.2 times of the molybdenum content (calculated by taking the amount of Mo as a reference weight) in the mother liquor, and filtering to obtain calcium molybdate CaMoO4And (5) producing the product.
2. The production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method according to claim 1, which is characterized in that: in the step of weighing and mixing the materials, the specified raw material ratio (by weight) is as follows:
waste aluminium-based molybdenum catalyst (V-containing by conversion)2O5Amount of) 1 part of (A) a,
natrii sulfas (Na)2SO4) 0.8-0.9 portion.
3. The production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method according to claim 1 or 2, wherein the production process comprises the following steps: in the step of precipitating and extracting molybdenum, calcium chloride CaCl is added under the stirring condition2Molybdenum deposition reaction is carried out, and calcium chloride CaCl is controlled2The adding amount of the calcium molybdate CaMoO is 1-1.5 times of the molybdenum content (calculated by the weight of Mo) in the mother liquor, and the calcium molybdate CaMoO is obtained by filtering4And (5) producing the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100217255A CN1557978A (en) | 2004-02-02 | 2004-02-02 | Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100217255A CN1557978A (en) | 2004-02-02 | 2004-02-02 | Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1557978A true CN1557978A (en) | 2004-12-29 |
Family
ID=34352012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004100217255A Pending CN1557978A (en) | 2004-02-02 | 2004-02-02 | Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1557978A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383289C (en) * | 2005-12-22 | 2008-04-23 | 中国铝业股份有限公司 | Vanadium removal for electrolytic stoste in metal gallium electrolysis |
| CN102191378A (en) * | 2010-03-15 | 2011-09-21 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN102586606A (en) * | 2011-10-13 | 2012-07-18 | 虹京环保有限公司 | Method for recovering rare earth, vanadium and nickel from waste FCC/ROC catalyst containing vanadium and nickel |
| CN101517104B (en) * | 2006-09-14 | 2013-01-16 | 雅宝荷兰有限责任公司 | Process for recovering group vi-b metals from spent catalysts |
| CN103160690A (en) * | 2011-12-14 | 2013-06-19 | 虹京环保有限公司 | Method for recovering metal oxide from SCR denitration waste catalyst |
| US8657917B2 (en) | 2011-05-06 | 2014-02-25 | Hong Jing Metal Corporation | Method for recycling metals from waste molybdic catalysts |
| CN103667680A (en) * | 2013-12-12 | 2014-03-26 | 攀枝花市柱宇钒钛有限公司 | Leaching technology for tailings clinker containing vanadium |
| CN106350680A (en) * | 2016-08-31 | 2017-01-25 | 大连博融新材料股份有限公司 | Method for extracting valuable metals from petroleum ash through sodium salt roasting |
| CN107500352A (en) * | 2017-08-26 | 2017-12-22 | 袁安会 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
| CN111534693A (en) * | 2020-04-30 | 2020-08-14 | 广东省资源综合利用研究所 | Resource recovery processing method for smelting wastewater precipitation slag |
| CN113582230A (en) * | 2021-08-14 | 2021-11-02 | 信丰华锐钨钼新材料有限公司 | Method for selectively removing phosphorus in sodium molybdate solution by using calcium chloride and sodium carbonate |
| CN113621834A (en) * | 2021-08-28 | 2021-11-09 | 信丰华锐钨钼新材料有限公司 | Method for selectively dephosphorizing molybdenum and phosphorus mixed solution |
| CN114574699A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院过程工程研究所 | Method for preparing ammonium metavanadate and ammonium molybdate from vanadium-molybdenum-containing solution |
-
2004
- 2004-02-02 CN CNA2004100217255A patent/CN1557978A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383289C (en) * | 2005-12-22 | 2008-04-23 | 中国铝业股份有限公司 | Vanadium removal for electrolytic stoste in metal gallium electrolysis |
| CN101517104B (en) * | 2006-09-14 | 2013-01-16 | 雅宝荷兰有限责任公司 | Process for recovering group vi-b metals from spent catalysts |
| CN102191378A (en) * | 2010-03-15 | 2011-09-21 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN102191378B (en) * | 2010-03-15 | 2013-12-18 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| US8657917B2 (en) | 2011-05-06 | 2014-02-25 | Hong Jing Metal Corporation | Method for recycling metals from waste molybdic catalysts |
| CN102586606A (en) * | 2011-10-13 | 2012-07-18 | 虹京环保有限公司 | Method for recovering rare earth, vanadium and nickel from waste FCC/ROC catalyst containing vanadium and nickel |
| CN103160690A (en) * | 2011-12-14 | 2013-06-19 | 虹京环保有限公司 | Method for recovering metal oxide from SCR denitration waste catalyst |
| CN103160690B (en) * | 2011-12-14 | 2015-03-11 | 虹京环保有限公司 | Method for recovering metal oxide from SCR denitration waste catalyst |
| CN103667680A (en) * | 2013-12-12 | 2014-03-26 | 攀枝花市柱宇钒钛有限公司 | Leaching technology for tailings clinker containing vanadium |
| CN103667680B (en) * | 2013-12-12 | 2016-07-06 | 攀枝花市柱宇钒钛有限公司 | Containing vanadium tailing soil grog extract technology |
| CN106350680A (en) * | 2016-08-31 | 2017-01-25 | 大连博融新材料股份有限公司 | Method for extracting valuable metals from petroleum ash through sodium salt roasting |
| CN106350680B (en) * | 2016-08-31 | 2018-10-26 | 大连博融新材料股份有限公司 | A method of sodium roasting extracts valuable metal from oil burnning ash |
| CN107500352A (en) * | 2017-08-26 | 2017-12-22 | 袁安会 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
| CN107500352B (en) * | 2017-08-26 | 2019-06-25 | 锦州集信实业有限公司 | A kind of method that low-temperature precipitation produces high-purity ammonium vanadate |
| CN111534693A (en) * | 2020-04-30 | 2020-08-14 | 广东省资源综合利用研究所 | Resource recovery processing method for smelting wastewater precipitation slag |
| CN111534693B (en) * | 2020-04-30 | 2021-04-30 | 广东省科学院资源综合利用研究所 | Resource recovery processing method for smelting wastewater precipitation slag |
| CN114574699A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院过程工程研究所 | Method for preparing ammonium metavanadate and ammonium molybdate from vanadium-molybdenum-containing solution |
| CN114574699B (en) * | 2020-12-01 | 2024-03-12 | 中国科学院过程工程研究所 | Method for preparing ammonium metavanadate and ammonium molybdate from vanadium-molybdenum-containing solution |
| CN113582230A (en) * | 2021-08-14 | 2021-11-02 | 信丰华锐钨钼新材料有限公司 | Method for selectively removing phosphorus in sodium molybdate solution by using calcium chloride and sodium carbonate |
| CN113582230B (en) * | 2021-08-14 | 2023-08-15 | 信丰华锐钨钼新材料有限公司 | Method for selectively removing phosphorus in sodium molybdate solution by using calcium chloride and sodium carbonate |
| CN113621834A (en) * | 2021-08-28 | 2021-11-09 | 信丰华锐钨钼新材料有限公司 | Method for selectively dephosphorizing molybdenum and phosphorus mixed solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1040029C (en) | Hydrometallurgical process for the recovery of precious metal values from precious metal ores with thiosulfate lixiviant | |
| CN1020112C (en) | Hydrocracking of heavy oil in presence of ultrafine iron sulphate | |
| CN1052265C (en) | Chloride assisted hydrometallurgical extraction of metal | |
| CN1557978A (en) | Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method | |
| CN1775371A (en) | Sulfogen ore impurity-removing, purifying and flotation process | |
| CN1926071A (en) | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus | |
| CN1904094A (en) | Method of extracting gold and silver from arsenic containing aurin ore | |
| CN1842608A (en) | Iron oxide precipitation from acidic iron salt solutions | |
| CN1008118B (en) | Prepn. of znso4 and active zno from zinc ore by entire wet-process | |
| CN1650036A (en) | Process for extracting platinum group metals | |
| CN1257295C (en) | Production method for extracting nickel by pyrogenic process | |
| CN86100354A (en) | Be used for trapping agent of plumbous zinc ore selective flotation and preparation method thereof | |
| CN1903769A (en) | Preparation method of magnesium calcium clinker | |
| CN1042349C (en) | Upgrading titaniferous materials | |
| CN1133752C (en) | Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation | |
| CN114031500A (en) | Preparation process of dimethyl carbonate and catalyst thereof | |
| CN1179057C (en) | Method for upgrading steel plant dust | |
| CN1314818C (en) | Method for extracting rare metal from waste and old carbide alloy | |
| CN1224723C (en) | Processing method for industrial waste material | |
| CN85100187A (en) | Process for chemcial separation of phosphate ore | |
| CN1014804B (en) | Process for treatment of ores or concentrates of lead sulfuride and/or lead-zinc sulfuride | |
| CN1234889C (en) | Extraction of platinum family metals and Cu, Ni and Co from sulfide ore or floated concentrate of platinum family metals | |
| CN86106873A (en) | Silver ore complete wet process for producing sponge silver and Silver Nitrate | |
| CN102534257A (en) | Novel bismuth smelting separation method | |
| CN102126735B (en) | Method for extracting tschermigite from coal gangue or stone coal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |